Charge transfer complexes with ferrocenes, their preparation and the use thereof

ABSTRACT

Charge transfer complexes of formula I 
     
         [A].sub.2.sup.⊖ B.sup.⊕                        (I), 
    
     wherein 
     a) A is a compound of formula II or a mixture of compounds of formula II ##STR1## wherein the R substituents are identical and are H or C 1  -C 4  alkyl, or the adjacent R substituents, taken together, are --(CH 2 ) 3  -- or --(CH 2 ) 4  --; R 1  is H or C 1  -C 4  alkyl; and X 1  is =N--CN, and X 2 , X 3  and X 4  are =O or =N--CN, and 
     b) B is a ferrocene or an indenyl derivative whose reduction potential E 1/2  is &lt;0.41 V, based on the standard calomel electrode. 
     The complexes are electric conductors with which polymers can be provided with an antistatic treatment or converted into electric conductors.

The present invention relates to charge transfer complexes (hereinafterabbreviated to CT complexes) of pentacenecyanoimine derivatives aselectron acceptors and ferrocene derivatives as electron donors; to aprocess for their preparation; to compositions comprising a plasticsmaterial and such a CT complex; and to the use of said CT complexes aselectric conductors, conveniently for making electrically conductivefilms, foils or coatings. These CT complexes are radical cation salts.

Powdered CT complexes of tetra-substituted pentacenecyanoimine andtetrathiofulvalene as electron donors having a conductivity of about 6S/cm are described in Synthetic Metals, 41-43, pages 2365-2375 (1991).

Further, 5,7,12,14-pentacenetetracyanoimine is described by L. Miller etal. in Chem. Mater. 2, pages 339-40 (1990) as electron acceptor for thepreparation of radical salts with alkali metals, typically sodium andpotassium.

U.S. Pat. No. 5,009,812 discloses antistatically treated and conductivepolymers that contain e.g. CT complexes of tetrathio-, tetraseleno- ortetratellurotetracenes as electron donors and halogens or oxygen aselectron acceptors. In these materials the CT complexes form needlenetworks in the polymer matrix. The preparation of these conductivepolymers necessitates the use of reagents that cause corrosion inmetallic machine parts, so that special measures have to be taken toprotect the machines. In addition, the poor solubility of chalcogenictetracenes makes rather high temperatures necessary for the preparationof the polymers. This is regarded as uneconomic and also requiresindustrial hygiene measures owing to the too high volatility of thereagents used. In addition, the use of tetraseleno- andtetratellurotetracenes is considered questionable for toxicologicalreasons.

Surprisingly, it has been found that pentacenecyanoimines and specificferrocene derivatives form CT complexes which, unexpectedly, even in thepresence of binders, crystallise in needle form, have a highconductivity and exert virtually no corrosive action on the metallicparts of processing machines. The starting compounds are also soluble inless polar organic solvents so that no very high temperatures arerequired for the preparation of the CT complexes. The CT complexes havesuperior stability to moisture and heat.

In one of its aspects, the invention relates to CT complexes of formulaI

    [A].sub.2.sup.⊖ B.sup.⊕                        (I),

wherein

a) A is a compound of formula II or a mixture of compounds of formula II##STR2## wherein the R substituents are identical and are H or C₁ -C₄alkyl, or the adjacent R substituents, taken together, are --(CH₂)₃ --or --(CH₂)₄ --; R₁ is H or C₁ -C₄ alkyl; and X₁ is =N--CN, and X₂, X₃and X₄ are =O or =N--CN, and

b) B is a ferrocene or an indenyl derivative whose reduction potentialE_(1/2) is <0.41 V, based on the standard calomel electrode.

R and R₁ defined as alkyl may be methyl, ethyl, n- or isopropyl or n-,iso- or tert-butyl. Preferred alkyl radicals are methyl and ethyl. In apreferred embodiment of the invention, the R substituents are C₁ -C₄alkyl and the R₁ substituents are H, or the R₁ substituents are C₁ -C₄alkyl and the R substituents are H. Preferably R and R₁ are H, methyl orethyl. In a particularly preferred embodiment of the invention, R and R₁are H.

In another preferred embodiment of the invention, X₁ and X₄ are =N--CNand X₂ and X₃ are =O or =N--CN, or X₂ and X₃ are =N--CN and X₁ and X₄are =O or =N--CN. The most preferred meaning of X₁, X₂, X₃ and X₄ is=N--CN.

The ferrocenyl derivative and the indenyl derivative preferably have areduction potential of less than or equal to 0.32 V.

B is formula I may typically be Fe[R₂ ]₂, wherein R₂ is cyclopentadienylor indenyl which contain 1 to 5 or 1 to 7 substituents respectively,selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₁-C₆ hydroxyalkyl, amino-C₁ -C₆ alkyl, primary or secondary amino-C₁ -C₆-alkyl containing 1 to 12 carbon atoms in the primary amino group and 2to 12 carbon atoms in the secondary amino group, NH₂, primary aminocontaining 1 to 12 carbon atoms, or secondary amino containing 2 to 12carbon atoms.

Alkyl may be linear or branched and contains preferably 1 to 4 carbonatoms. Typical examples are methyl, ethyl, n- or isopropyl, n-, iso- ortert-butyl, pentyl and hexyl. Ethyl and, more particularly, methyl arepreferred.

Alkoxy may be linear or branched and contains preferably 1 to 4 carbonatoms. Typical examples are methoxy, ethoxy, n- or isopropoxy, n-, iso-or tert-butoxy, pentoxy and hexoxy. Ethoxy and, more particularly,methoxy are preferred.

Hydroxyalkyl may be linear or branched and contains preferably 1 to 4carbon atoms. Typical examples are hydroxymethyl, hydroxyethyl, n- oriso-hydroxypropyl, n-, iso- or tert-hydroxybutyl, hydroxypentyl andhydroxyhexyl. Hydroxyethyl and, more particularly, hydroxymethyl arepreferred.

Aminoalkyl may be linear or branched and contains preferably 1 to 4carbon atoms. Typical examples are aminomethyl, aminoethyl, n- oriso-aminopropyl, n-, iso- or tert-aminobutyl, aminopentyl andaminohexyl. Aminoethyl and, more particularly, aminomethyl arepreferred.

Primary and secondary aminoalkyl may be linear or branched and containspreferably 1 to 4 carbon atoms. The primary amino group preferablycontains one C₁ -C₆ alkyl group, most preferably one C₁ -C₄ alkyl group,and the secondary amino group contains preferably two C₁ -C₆ alkylgroups, most preferably one C₁ -C₄ alkyl group. Especially preferredalkyl groups are methyl and ethyl. Typical examples aremethylaminomethyl, dimethylaminomethyl, diethylaminomethyl,methylaminoethyl, dimethylaminoethyl, or diethylaminopropyl,dimethylaminobutyl, diethylaminopentyl and dimethylaminohexyl. Preferredgroups are methylaminoethyl, dimethylaminomethyl, ethylaminoethyl,diethylaminoethyl, methylaminomethyl, dimethylaminomethyl,ethylaminomethyl and diethylaminomethyl.

Primary amino preferably contains 1 to 6 carbon atoms and secondaryamino preferably contains 2 to 6 carbon atoms. Preferably primary andsecondary amino contains C₁ -C₄ alkyl, typically methyl, ethyl, n- orisopropyl or n-, iso- or tert-butyl. Typical examples are methylamino,dimethylamino, ethylamino, diethylamino, n- and isopropylamino, di-n-and diisopropylamino, n-, iso- and tert-butylamino, di-n- anddiisobutylamino.

In a preferred embodiment of the invention, cyclopentadienyl and indenylare substituted by C₁ -C₄ alkyl, most preferably by methyl. In aparticularly preferred embodiment of the invention, A in formula I is5,7,12,14-pentacenetetracyanoimine and B in formula I is ferrocene whosecyclopentadienyl groups are substituted by 1 to 5 C₁ -C₄ alkyl groups.

Cyclopentadienyl preferably contains at least 2 and, most preferably, atleast 3 substituents. Indenyl preferably contains 1 to 7 and, mostpreferably, 1 to 5 substituents.

Typical examples of B in formula I are dimethylferrocene,tetramethylferrocene, hexamethylferrocene, octamethylferrocene anddecamethylferrocene. The compound of formula II is preferably5,7,12,14-pentacenetetracyanoimine which is in pure form or contains upto 10% by weight, based on the total mixture, of compounds of formula IIin which one or two cyanoimine groups are replaced by oxygen. Especiallypreferred CT complexes of formula I are those of5,7,12,14-pentacenetetracyanoimine and dimethylferrocene,tetramethylferrocene, hexamethylferrocene, octamethylferrocene anddecamethylferrocene.

In another of its aspects, the invention reletes to a process for thepreparation of CT complexes of formula I, which comprises reactingequimolar amounts of a ferrocene derivative B and a pentacenecyanoimineof formula II in an inert organic solvent. Equimolar amounts means thatabout 1 equivalent of the ferrocene derivative B is reacted with about 2equivalents of the pentacenecyanoimine of formula II to form the 2:1complexes.

The ferrocene derivatives are known, some are commercially available orthey can be prepared by known standard methods. The preparation of5,7,12,14-pentacenetetracyanoimine is described by L. L. Miller inSynthetic Metals, 41-43, pages 2365-2375 (1991). The startingunsubstituted or substituted 5,7,12,14-pentacenetetrones are obtainableby a process described by W. H. Mills et al. in J. Chem. Soc. 101, page2194 (1912). The 5,7,12,14-pentacenetetracyanoimines can be purified byconventional methods, conveniently by recrystallisation orchromatographic methods. If no special protective measures are taken,for example anhydrous conditions, cyanoimine groups can be replaced byoxygen, but without adversely affecting the formation of the desired CTcomplexes.

The inventive process is conveniently carried out at elevatedtemperature, typically at 30°-200° C., preferably at 50°-100° C.

Suitable solvents are typically non-polar, polar and aprotic solventswhich may be used singly or in mixtures of at least two solvents.Typical examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane,ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethylor diethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether), halogenated hydrocarbons (methylene chloride,chloroform, 1,2-dichlorethane, 1,1,1-trichloroethane,1,1,2,2-tetrachloroethane), carboxylates and lactones (ethyl acetate,methyl propionate, ethyl benzoate, 2-methoxyethylacetate,γ-butyrolactone, δ-valerolactone, pivalolactone), carboxamides andlactams (N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, tetramethylurea, hexamethylphosphoric triamide,γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone,N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones(dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tetramethylenesulfone), tertiary amines (N-methylpiperidine, N-methylmorpholine),substituted benzenes (benzonitrile, chlorobenzene, o-dichlorobenzene,1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene), nitriles(acetonitrile, propionitrile) and aliphatic or cycloaliphatichydrocarbons (petroleum ether, pentane, hexane, cyclohexane andmethylcyclohexane). Suitable solvents are also aromatic-aliphaticethers, for example methyl or ethyl phenyl ether.

The CT complexes obtainable by the process of this invention areobtained in great purity and, after filtration, need only be washed withsolvents. Ordinarily they are obtained as black needle-shaped crystalswhich have conductivities of more than 0.1 S/cm. They therefore haveexcellent suitability for use as electric conductors. Depending on thetype of CT complex and on the amount added it is possible to obtainelectrically conductive or antistatically treated plastics byincorporating these CT complexes in plastics materials, the CT complexbeing present in the plastics matrix as a network of crystal needles.Depending on the concentration of CT complex in the plastics matrix,very fine meshed needle networks can be obtained.

In yet another of its aspects, the invention relates to a compositioncomprising a) a thermosetting, thermoplastic or structurally crosslinkedpolymer and b) a CT complex of formula I in the form of a network ofcrystal needles in the polymer matrix.

The composition may contain the CT complex in a concentration of 0.01 to30% by weight, preferably of 0.01 to 20% by weight, more particularly of0.01 to 10% by weight and, most preferably, of 0.1 to 5% by weight,based on said composition.

The thermoplastic polymers may conveniently be selected from among thefollowing polymers, copolymers or mixtures of these polymers:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, polymethylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for example ofcyclopentene or norbornene, polyethylene (which can be uncrosslinked orcrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers, ethylene/hexenecopolymers, ethylene/ethylpentene copolymers, ethylene/heptenecopolymers, ethylene/octene copolymers, propylene/isobutylenecopolymers, ethylene/but-1-ene copolymers, propylene/butadienecopolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylatecopolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinylacetate or ethylene/acrylic acid copolymers and the salts thereof(ionomers), as well as terpolymers of ethylene with propylene and adiene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene;and also mixtures of such polymers with one another and with polymersmentioned in 1) above, for example polypropylene/ethylene-propylenecopolymers, LDPE/ethylene-vinyl acetate copolymers (EVA),LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EVA andalternating or random polyalkylene/carbon monoxide copolymers andmixtures thereof with other polymers, for example polyamides.

3a. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (for example tackifiers) and mixtures ofpolyalkylenes and starch.

4. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

5. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/maleic anhydride,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylatestyrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthfrom styrene copolymers and another polymer, for example from apolyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer;and block copolymers of styrene, for example styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene and maleic anhydride ormaleimide on polybutadiene; styrene, acrylonitrile and maleic anhydrideor maleimide on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene, styrene and alkyl acrylates ormethacrylates on polybutadiene, styrene and acrylonitrile onethylene/propylene/diene terpolymers, styrene and acrylonitrile onpolyacrylates or polymethacrylates, styrene and acrylonitrile onacrylate/butadiene copolymers, as well as mixtures thereof with thecopolymers listed in 5), for example the copolymer mixtures known asABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or chlorosulfonated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,polymers of halogenated vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof, for example vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinylacetate copolymers.

8. Polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates and polymethacrylates, polymethyl methacrylateimpact-modified with butyl acrylate, polyacrylamides andpolyacrylonitrile.

9. Copolymers of the monomers mentioned in 8) with each other or withother unsaturated monomers, for example acrylonitrile/butadiene,acrylonitrile/alkyl acrylate, acrylonitrile/alkoxyalkyl acrylate oracrylonitrile/vinyl halide copolymers or acrylonitrile/alkylmethacrylate/butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines, or acylderivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis(glycidyl) ethers.

12. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides and mixtures thereof with styrenepolymers or polyamides.

14. Polyurethanes derived from polyethers, polyesters orhydroxyl-terminated polybutadienes on the one hand and aliphatic oraromatic polyisocyanates on the other, as well as precursors thereof.

15. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,12/12, polyamide 11, polyamide 12, aromatic polyamides obtained bycondensation of m-xylene diamine and adipic acid; polyamides preparedfrom hexamethylenediamine and isophthalic or/and terephthalic acid andoptionally an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also copolymers of the aforementioned polyamideswith polyolefins, olefin copolymers, ionomers or chemically bonded orgrafted elastomers; or with polyethers, as with polyethylene glycols,polypropylene glycols or polytetramethylene glycols; polyamides orcopolyamides modified with EPDM or ABS; polyamides condensed duringprocessing (RIM polyamide systems).

16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate,poly[2,2,-(4-hydroxyphenyl)propane]terephthalate andpolyhydroxybenzoates as well as block copolyether esters derived fromhydroxyl-terminated polyethers; and also polyester modified withpolycarbonates or MBS.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Polyethers of diglycidyl compounds, typically diglycidyl ethers anddiols, e.g. of the diglycidyl ether of bisphenol A and bisphenol A.

21. Natural polymers, such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, such as cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

22. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPE/HIPS, PPE/PA 66 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

Preferred thermoplastic polymers are polyolefins, polystyrene, polyvinylchloride, polyvinylidene chloride, polyvinylidene fluoride,polyacrylates, polymethacrylates, polyamides, polyesters,polycarbonates, aromatic polysulfones, aromatic polyethers, aromaticpolyether sulfones, polyimides and polyvinyl carbazole.

The thermosetting and structurally crosslinked polymers may be typicallythe following polymers:

1. Crosslinked polymers which are derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

2. Drying and non-drying alkyd resins.

3. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

4. Crosslinkable acrylic resins derived from substituted acrylic esterssuch as epoxy acrylates, urethane acrylates or polyester acrylates.

5. Alkyd resins, polyester resins or acrylate resins which arecross-linked with melamine resins, urea resins, polyisocyanates or epoxyresins.

6. Rubber derived from crosslinked polydienes, for example butadiene orisoprene; silicon rubber.

7. Crosslinked epoxy resins which are derived from polyepoxides, forexample from bisglycidyl ethers or from cycloaliphatic diepoxides, andwhich may contain a hardener as crosslinking agent or which arecrosslinked thermally using curing accelerators or by irradiation.

Among the crosslinked polymers, crosslinked epoxy resins are preferredwhich, as polyepoxides, are derived preferably from glycidyl compoundswhich contain on average two epoxy groups in the molecule. Particularlysuitable glycidyl compounds are those which contain two glycidyl groups,β-methylglycidyl groups or 2,3-epoxycyclopentyl groups attached to ahetero atom (e.g. sulfur, preferably oxygen or nitrogen), in particularbis(2,3-epoxycyclopentyl) ether; diglycidyl ethers of polyhydricaliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols,such as polypropylene glycols; diglycidyl ethers of cycloaliphaticpolyols, such as 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethersof polyhydric phenols, such as resorcinol, bis(p-hydroxyphenyl)methane,2,2-bis(p-hydroxyphenyl)propane (=diomethane),2,2-bis(4'-hydroxy-3',5'-dibromophenyl)propane,1,3-bis(p-hydroxyphenyl)ethane; bis(β-methylglycidyl) ethers of theabove dihydric alcohols or dihydric phenols; diglycidyl esters ofdicarboxylic acids, such as phthalic acid, terephthalic acid, Δ₄-tetrahydrophthalic acid and hexahydrophthalic acid; N,N-diglycidylderivatives of primary amines and amides and heterocyclic nitrogen baseswhich contain two N-atoms, and N,N'-diglycidyl derivatives ofdisecundary diamides and diamines, such as N,N-diglycidylaniline,N,N-diglycidyltoluidine, N,N-diglycidyl-p-aminophenyl methyl ether,N,N'-dimethyl-N,N'-diglycidylbis(p-aminophenyl)methane;N',N"-diglycidyl-N-phenyl-isocyanurate; N,N'-diglycidyl ethyleneurea;N,N'-diglycidyl-5,5-dimethylhydantoin,N,N'-diglycidyl-5-isopropyl-hydantoin,N,N-methylenebis(N',N'-diglycidyl-5,5-dimethylhydantoin),1,3-bis(N-glycidyl-5,5-dimethylhydantoin)-2-hydroxypropane;N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil, triglycidylisocyanurate.

A preferred group of epoxy resins comprises glycidylated novolaks,hydantoins, aminophenols, bisphenols and aromatic diamines orcycloaliphatic epoxy compounds. Particularly preferred epoxy resins areglycidylated cresol novolaks, bisphenol A and bisphenol F diglycidylether, hydantoin-N,N'-bisglycide, p-aminophenol triglycide,diaminodiphenylmethane tetraglycide, vinylcyclohexene dioxide,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or mixturesthereof.

Further suitable epoxy resins are prereacted adducts of such epoxycompounds with epoxy hardeners, for example an adduct of bisphenol Adiglycidyl ether and bisphenol A, or adducts which have been prereactedwith oligoesters which carry two terminal carboxyl groups and epoxides.

Suitable hardeners for epoxy resins are acid or basic compounds.Illustrative examples of suitable hardeners are: polyhydric phenols(resorcinol, 2,2-bis(4-hydroxyphenyl)propane) or phenol-formaldehyderesins; polybasic carboxylic acids and the anhydrides thereof, such asphthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalicanhydride, 4-methylhexahydrophthalic anhydride,3,6-endomethylene-tetrahydrophthalic anhydride,4-methyl-3,6-endomethylen-tetrahydrophthalic anhydride (methylnadicanhydride), 3,4,5,6,7,7-hexachloroendomethylene-tetrahydrophthalicanhydride, succinic anhydride, adipic anhydride, trimethyladipicanhydride, sebacic anhydride, maleic anhydride, dodecylsuccinicanhydride, pyromellitic dianhydride, trimellitic anhydride,benzophenonetetracarboxylic dianhydride, or mixtures of such anhydrides.

A preferred group of hardeners comprises novolaks and polycarboxylicanhydrides.

The epoxy resins can also be additionally cured with curing acceleratorsor only with thermal curing catalysts. Exemplary of curing acceleratorsand catalysts are 3-ethyl-4-methylimidazole, triamylammonium phenolate;mono- or polyphenols (phenol, diomethane, salicyclic acid); borontrifluoride and the complexes thereof with organic compounds, such asboron trifluoride ether complexes and boron trifluoride amine complexes(BF₃ /monoethylamine complex); phosphoric acid and triphenylphosphite.

Curing accelerators and catalysts are normally added in an amount of 0.1to 10% by weight, based on the epoxy resin. Hardeners for epoxy resinsare normally used in equimolar amounts, based on the epoxy groups andfunctional groups of a hardener.

Further additives for enhancing processing properties, the mechanical,electrical and thermal properties, surface properties and lightstability can be blended into the novel formulation. Exemplary of suchadditives are finely particulate fillers, reinforcing fillers,plasticisers, lubricants and mould release agents, adhesion promoters,antistatic agents, antioxidants, heat and light stabilisers, pigmentsand dyes.

In a preferred embodiment, the novel compositions are shaped tomouldings, films, sheets, fibres, or to coatings on at least one surfaceof a substrate.

In yet another of its aspects, the invention relates to a process forthe preparation of novel compositions, which comprises (a) blending a CTcomplex of formula I into a thermoplastic polymer, (b) blending a CTcomplex of formula I with at least one component of a thermosetting orstructurally crosslinkable polymer and then polymerising the blend,together with a further optional component, to a thermosetting orstructurally crosslinked polymer, or (c) dissolving a compound offormula II or a ferrocene derivative B, together with a thermoplasticpolymer or with at least one component of a thermosetting orstructurally crosslinkable polymer in an organic solvent, mixing thissolution, together with further optional components of a thermosettingor structurally crosslinkable polymer with a solution of a ferrocenederivative B or a compound of formula II, removing the solvent andpolymerising curable mixtures to a thermosetting or structurallycrosslinked polymer. The process can be combined with a shaping process.

The preparation of the novel composition can be carried out by methodsknown in plastics technology. In shaping techniques for polymers,typically casting, compression moulding, injection moulding andextrusion, the CT complex itself can be added to a thermoplastic polymeror to at least one component of a thermosetting plastic to form asuspension, or separately to each component (e.g. the epoxy resin andthe hardener) to form a solution or suspension, such that after shapingthe CT complex crystallises and precipitates in the form of needlesduring cooling and the needles form a network in a polymer matrix.

In a particularly preferred embodiment, the novel composition is in theform of a film or foil or a coating on at least one surface of asubstrate. Such embodiments are conveniently prepared by suspendingand/or dissolving a thermoplastic polymer or at least one startingmaterial of a thermosetting polymer or a structurally crosslinkedpolymer in an inert solvent together with a CT complex of formula I, ordissolving a thermoplastic polymer or at least one starting material ofa thermosetting polymer or a structurally crosslinked polymer togetherwith a compound of formula II or a ferrocene derivative B, and thenmixing the solution or suspension with a solution of the ferrocenederivative B or a compound of formula II, and subsequently applying themixture by known coating techniques to a substrate which may bepreheated, and thereafter removing the solvent by heating, such thatcrosslinkable mixtures can then be fully cured. Self-supporting filmsand foils are obtained by peeling the coating from the substrate or byextrusion.

Examples of suitable substrates are glass, metals, plastics, mineral andceramic materials, wood and paper. The substrates may be of any externalshape and are typically mouldings, filaments, fibres, fabrics, bars,pipes, ribbons, sheets, boards, rolls or casings.

Suitable coating techniques are typically brushing, rolling, doctorcoating, casting, spin coating, curtain coating and spraying. Sprayingmethods are especially preferred, as on the one hand very thin anduniform layers with substantially isotropic, very fine-mesh andhomogeneous networks are obtainable from crystal needles of the CTcomplexes and, on the other, the size of the crystal needles and themesh width of the networks can be controlled by the droplet size, evenwhen suspensions are sprayed.

Suitable inert solvents for polymers and starting materials for polymersare typically polar and, preferably, aprotic solvents, which may be usedsingly or in mixtures of at least two solvents. Representative examplesof such solvents are: ethers (dibutyl ether, tetrahydrofuran, dioxane,ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethylor diethyl ether, diethylene glycol diethyl ether, triethylene glycoldimethyl ether), halogenated hydrocarbons (methylene chloride,chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane,1,1,2,2-tetrachloroethane), carboxylates and lactones (ethyl acetate,methyl propionate, ethyl benzoate, 2-methoxyethyl acetate,γ-butyrolactone, δ-valerolactone, pivalolactone), carboxamides andlactams (N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, tetramethylurea, hexamethylphosphoric triamide,γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone,N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones(dimethyl sulfone, diethyl sulfone, trimethylene sulfone, tetramethylenesulfone), tertiary amines (N-methylpiperidine, N-methylmorpholine)substituted benzenes (benzonitrile, chlorobenzene, o-dichlorobenzene,1,2,4-trichlorobenzene, nitrobenzene, toluene, xylene) and nitriles(acetonitrile, propionitrile). Further suitable solvents arearomatic-aliphatic ethers such as methyl or ethyl phenyl ether. Suitablesolvents for the compounds of formula II and the ferrocene derivatives Bhave been mentioned hereinabove.

The coating techniques can conveniently be carried out by dissolving theindividual components separately and combining them just beforeapplication of the chosen technique. However, it is also possible toprepare two solutions of the components, for example of polymer solutionand ferrocene derivative B or of a compound of formula II, and solutionof a compound of formula II or of a ferrocene derivative B together witha polymer, or to combine all the components in one solution. In thislast mentioned case, the CT complexes can crystallise out already priorto coating; but this has virtually no effect on the desired quality ofthe coating.

The solutions are preferably heated, conveniently to 30°-200° C. It isuseful to heat the substrate as well to accelerate the removal of thesolvent, which is normally effected in the temperature range from 50° to150° C., preferably 50° to 100° C., until the coating is dry. If it isdesired to detach the coatings to give self-supporting films or sheets,the substrate can be treated with antiblocking agents prior to coating.

An alternative coating method comprises suspending the CT complexes,which are obtained as needle-shaped crystals, in a solution of a polymeror of starting materials for obtained as needle-shaped crystals, in asolution of a polymer or of starting materials for thermosettingpolymers, then coating a substrate and afterwards removing the solvent,and, if appropriate, thereafter effecting a cure to form thethermosetting polymers. It is also possible to prepare dry powdermixtures from polymer powders or solid starting materials forthermosetting polymers and the CT complexes, and to process thesemixtures in coating or electrostatic coating methods to layers onsubstrates. Networks of crystal needles in a polymer matrix are alsoobtained in these alternative methods.

It is also possible to produce pure layers of networks of crystalneedles of the CT complexes on a substrate by applying to a substratesolutions or suspensions of the CT complexes in a solvent and afterwardsevaporating the solvent. Such layers can be electrochemically metallisedto enhance the conductivity, conveniently with Cu, Pt or Pd. It can beuseful to provide such pure layers with a protective coating of apolymer or to coat the pure layers subsequently with a polymer.

The layer thicknesses can vary over a wide range, depending on thechoice of coating method. Spray methods give very thin layers, whereasthicker layers can also be obtained with brushing and casting methods.The layer thicknesses can be typically from 0.01 to 5000 μm, preferablyfrom 0.1 to 1000 μm and, most preferably, from 0.1 to 500 μm.

Depending on the choice of polymer, the novel compositions are opaque ortransparent and have outstanding electrical properties. Thus,surprisingly, the coatings and mouldings have an excellent dischargecapacity which, for heterogeneous materials, is otherwise difficult toachieve or cannot be achieved at all. The compositions are thereforeespecially suitable for use for making antistatically treated mouldedparts for the electrostatic screening of components or for makingantistatically treated mouldings. The high conductivities also permitthe use of the novel compositions as electric conductors, for example aselectrodes for display elements or electronic components as well ascharge carriers in capacitors. The compositions also have excellentmechanical strength and performance properties. The compositions canalso be prepared at comparatively low temperatures and have theadditional advantage of causing no or only insignificant corrosion inmetallic machine parts. Furthermore, they have good stability to theaction of heat and/or moisture.

Further objects of the invention are the use of the novel chargetransfer complexes of formula I as electric conductors; the use of thenovel compositions as antistatically treated moulded parts for theelectronic screening of components or as antistatically treatedmouldings; the use of the novel compositions as electric conductors; theuse of the novel compositions as electrode material; and the use of thenovel compositions in the form of films or foils as charge carriers incapacitors.

The following Examples illustrate the invention in more detail.

A) PREPARATION OF THE CT COMPLEXES Example A1: Preparation of a CTcomplex from dimethyl ferrocene and 5,7,12,14-pentacenetetracyanoimine

A solution warmed to 70° C. of 261 mg (0.6 mmol) of5,7,12,14-tetracenetetracyanoimine in 90 ml of γ-butyrolactone is addedto a solution warmed to the same temperature of 64 mg (0.3 mmol) ofdimethylferrocen in 8 ml of γ-butyrolactone. The resultant greensolution is allowed to stand for 72 hours at room temperature, duringwhich time black crystal needles precipitate. The crystals are isolatedby filtration, washed with hexane and then dried under a high vacuum togive 60 mg (18%) of the title compound having a conductivity (measuredby the 4 point method using a pressed pellet) of 2.0 S/cm. Elementalanalysis found (calcd.): C 70.94 (70.98); H 3.26 (3.16); N 20.42(20.69); Fe 5.14 (5.16).

Example A2: Preparation of a CT complex from hexamethylferrocene and5,7,12,14-pentacenetetracyanoimine

A solution warmed to 80° C. of 1.203 g (2.769 mmol) of5,7,12,14-tetracenetetracyanoimine in 500 ml of 1,2-dichloroethan isadded to a solution warmed to the same temperature of 374 mg (1.385mmol) of hexamethylferrocene in 40 ml of 1,2-dichloroethane. Blackneedles crystallise immediately from the resultant green solution. Thesolution is allowed to cool first to room temperature and is then cooledto -5° C. The precipitate is isolated by filtration, washed with CH₂ Cl₂and then dried under a high vacuum to give the title compound in a yieldof 126 mg (61%). The pressed pellet conductivity is 1.0 S/cm. Elementalanalysis found (calcd.): C 71.05 (71.71); H 3.85 (3.72); N 19.88(19.68); Fe 4.63 (4.90). Decomposition temperature 217° C.

Example A3: Preparation of a CT complex from octamethylferrocene and5,7,12,14-pentacenetetracyanoimine

A solution warmed to 80° C. of 69 mg (0.230 mmol) of octamethylferrocenin 250 ml of 1,2-dichlorethane is added to a solution warmed to the sametemperature of 200 mg (0.460 mmol) of 5,7,12,14-pentacenetetracyanoiminein 150 ml of 1,2-dichlorethane. Black needles crystallise immediatelyfrom the resultant green solution. The solution is allowed to cool firstto room temperature and is then cooled to -5° C. The precipitate isisolated by filtration, washed with CH₂ Cl₂ and then dried under a highvacuum to give the title compound in a yield of 175 mg (65%). Thepressed pellet conductivity is 3.0 S/cm. Elemental analysis found(calcd.): C 71.48 (72.04); H 4.03 (3.97); N 18.76 (19.20); Fe 4.74(4.78). Decomposition temperature 242° C.

Example A4: Preparation of a CT complex from decamethylferrocene and5,7,12,14-pentacenetetracyanoimine

A solution warmed to 80° C. of 150 mg (0.345 mmol) of5,7,12,14-pentacenetetracyanoimine in 350 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 56 mg (0.173 mmol)of decamethylferrocene in 250 ml of 1,2-dichlorethane. Black needlescrystallise immediately from the resultant green solution. The solutionis allowed to cool first to room temperature and is then cooled to -5°C. The precipitate is isolated by filtration, washed with CH₂ Cl₂ andthen dried under a high vacuum to give the title compound in a yield of126 mg (61%). The pressed pellet conductivity is 1.0 S/cm. Elementalanalysis found (calcd.): C 71.81 (72.36); H 4.35 (4.22); N 18.15(18.75); Fe 4.67 (4.88). Decomposition temperature 243° C.

Example A5: Preparation of a CT complex of decamethylferrocene and5,7,12,14-pentacenetetracyanoimine,5,7,14-triacyanoimine-12-oxopentacene and 7,14-dicyanoimine-5,12-dioxopentacene

A solution warmed to 85° C. of 300 mg of a mixture of5,7,12,14-pentacenetetracyanoimine,5,7,14-triacyanoimine-12-oxopentacene and7,14-dicyanoimine-5,12-dioxopentacene in 70 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 113 mg ofdecamethylferrocene in 25 ml of 1,2-dichloroethane. Fine black needlescrystallise immediately from the resultant dark red solution. The batchis allowed to stand for a few hours at room temperature, the precipitateis isolated by filtration, washed with CH₂ Cl₂ and then dried under ahigh vacuum. A pellet of the CT complex has a conductivity of 0.52 S/cm.

Example A6: Preparation of a CT complex from tetramethylferrocene and5,7,12,14-pentacenetetracyanoimine

A solution warmed to 80° C. of 251 mg of5,7,12,14-pentacenetetracyanoimine in 300 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 70 mg oftetramethylferrocene in 70 ml of 1,2-dichloroethane. The resultantsolution is filtered and the filtrate is concentrated to a volume of 50ml. The precipitated green needles are isolated by filtration, washedwith methylene chloride and then dried to give 110 mg (34%) of the titlecompound with a pressed pellet conductivity of 1.42 S/cm.

B) USE EXAMPLES Example B1

A solution warmed to 70° C. of 4 mg of5,7,12,14-pentacenetetracyanoimine in 3 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 100 mg ofpolycarbonate and 1.5 mg of octamethylferrocene in 8 ml1,2-dichloroethane. Aliquots of the mixture are poured on to a glassplate and the solvent is evaporated at different temperatures. Theconductivity of the foils so obtained is measured.

    ______________________________________                                        Evaporation temperation (°C.)                                                             Conductivity (S/cm)                                        ______________________________________                                        40                 1.2                                                        45                 1.0                                                        50                 1.0                                                        ______________________________________                                    

Stability: The foils are immersed for 300 hours in water at roomtemperature and the conductivity is measured afterwards. Theconductivity is still high enough for the foils to be used forantistatic screening.

Example B2

A solution warmed to 70° C. of 4 mg of5,7,12,14-pentacenetetracyanoimine in 3 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 100 mg ofpolycarbonate and 1.5 mg of hexamethylferrocene in 8 ml1,2-dichloroethane. Aliquots of the mixture are poured on to a glassplate and the solvent is evaporated at different temperatures. Theconductivity of the foils so obtained is measured.

    ______________________________________                                        Evaporation temperature (°C.)                                                             Conductivity (S/cm)                                        ______________________________________                                        40                 1.1                                                        45                 1.0                                                        50                 0.4                                                        ______________________________________                                    

Stability: The foils are immersed for 300 hours in water at roomtemperature and the conductivity is measured afterwards. Theconductivity is still high enough for the foils to be used forantistatic screening.

Example B3

A solution warmed to 70° C. of 4 mg of a mixture of5,7,12,14-pentacenetetracyanoimine,5,7,14-triacyanoimine-12-oxopentacene and7,14-dicyanoimine-5,12-dioxopentacene in 3 ml of 1,2-dichloroethane isadded to a solution warmed to the same temperature of 100 mg ofpolycarbonate and 1.5 mg of decamethylferrocene in 8 ml of1,2-dichloroethane. Aliquots of the mixture are poured on to a glassplate and the solvent is evaporated at different temperatures. Theconductivity of the foils so obtained is measured.

    ______________________________________                                        Evaporation temperature (°C.)                                                             Conductivity (S/cm)                                        ______________________________________                                        30                 1.6 · 10.sup.-2                                   40                 4.5 · 10.sup.-2                                   45                 5.5 · 10.sup.-2                                   50                 3.5 · 10.sup.-2                                   60                 2.0 · 10.sup.-2                                   ______________________________________                                    

The foils are immersed for 500 hours at 85° C. and 85% humidity. Theyare still sufficiently conductive for use for antistatic screening.

Example B4

A solution of 5.7 mg of the complex of Example A2 and 100 mg ofpolycarbonate in 14 ml of anisole is prepared at 80° C. The solution ispoured on to a glass plate and the solvent is evaporated at 100° C. Theresultant film has a conductivity of 9×10⁻² S/cm.

Example B5

A solution warmed to 80° C. of 8.7 g of5,7,12,14-pentacenetetracyanoimine in 3 ml of toluene is added to asolution warmed to 80° C. of 100 mg of polystyrene and 2.7 mg ofhexamethylferrocene in 8 ml of toluene. The solution is poured on to aglass plate and the solvent is evaporated at 80° C. A conductivity of4.1×10⁻² S/cm is measured on the resultant foil.

Example B6

A solution warmed to 40° C. of 4.3 g of5,7,12,14-pentacenetetracyanoimine in 10 ml of methylene chloride isadded to a solution warmed to 40° C. of 100 mg of polycarbonate and 1.3mg of hexamethylferrocene in 18 ml of methylene chloride. The solutionis poured on to a glass plate and the solvent is evaporated at 40° C. Aconductivity of 1.2 S/cm is measured on the resultant foil.

Example B7

A solution warmed to 70° C. of 4.5 g of5,7,12,14-pentacenetetracyanoimine in 4 ml of dimethyl formamide isadded to a solution warmed to 70° C. of 200 mg of polysulfone and 1.5 mgof octamethylferrocene in 10 ml of dimethyl formamide. The solution ispoured on to a glass plate and the solvent is evaporated at 70° C. Aconductivity of 9.3×10⁻² S/cm is measured on the resultant foil.

Example 8

A solution warmed to 45° C. of 4 g of 5,7,12,14-pentacenetetracyanoiminein 4 ml of 1,2-dichloromethane is added to a solution warmed to 45° C.of 100 mg of polycarbonate and 1.5 mg of decamethylferrocene in 7 ml of1,2-dichloromethane. The solution is poured on to a glass plate and thesolvent is evaporated at 45° C. A conductivity of 5.4×10⁻² S/cm ismeasured on the resultant foil.

What is claimed is:
 1. A charge transfer complex of formula I

    (A).sub.2.sup.⊖ B.sup.⊕                        (I)

wherein a) A is a compound of formula II or a mixture of compounds offormula II ##STR3## wherein the R substituents are identical and are Hor C₁ -C₄ alkyl, or the adjacent R substituents, taken together,are--(CH₂)₃ -- or--(CH₂)₄ --; R₁ is H or C₁ -C₄ alkyl; and X₁ is N--CN,and X₂, X₃, and X₄ are O or N--CN, and b) B is a ferrocene derivativecompound of the formula Fe(R₂)₂, whereinR₂ is cyclopentadienyl orindenyl which contain 1 to 5 or 1 to 7 substituents respectively, thesubstituents being selected from the group consisting of C₁ -C₆ alkyl,C₁ -C₆ alkoxy, C₁ -C₆ hydroxyalkyl, NH₂, NH(C₁ -C₆ alkyl), or N(C₁ -C₆alkyl)₂ ; whereinthe reduction potential E_(1/2) of the ferrocenederivative compound is<0.41 V, based on the standard calomel electrode.2. A complex according to claim 1, wherein R is C₁ -C₄ alkyl and R₁ isH.
 3. A complex according to claim 1, wherein R₁ is C₁ -C₄ alkyl and Ris H.
 4. A complex according to claim 1, wherein R and R₁ as alkyl aremethyl or ethyl.
 5. A complex according to claim 1, wherein R and R₁ areH, methyl or ethyl.
 6. A complex according to claim 1, wherein R and R₁are H.
 7. A complex according to claim 1, wherein X₁ and X₄ are=N--CNand X₂ and X₃ are=O or=N--CN, or X₂ and X₃ are=N--CN and X₁ and X₄ are=Oor=N--CN.
 8. A complex according to claim 1, wherein X₁, X₂, X₃ and X₄are=N--CN.
 9. A complex according to claim 1, wherein the ferrocenylderivative B has a reduction potential of less than or equal to 0.32 V.10. A complex according to claim 1, wherein R₂ is cyclopentadienyl orindenyl which contain 1 to 5 or 1 to 7 substituents respectively, thesubstituents being selected from the group consisting of C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₁ -C₄ hydroxyalkyl, NH₂, NH(C₁ -C₄ alkyl), or N(C₁ -C₄alkyl)₂.
 11. A complex according to claim 1, wherein R₂ iscyclopentadienyl or indenyl which are substituted by C₁ -C₄ alkyl.
 12. Acomplex according to claim 11, wherein alkyl is methyl.
 13. A complexaccording to claim 1, wherein the ferrocenyl derivative B is selectedfrom the group consisting of dimethylferrocene, tetramethylferrocene,hexamethylferrocene, octamethylferrocene and decamethylferrocene.
 14. Acomplex according to claim 1, wherein A in formula I is5,7,12,14-pentacenetetracyanoimine and B is dimethylferrocene,tetramethylferrocene, hexamethylferrocene, octamethylferrocene ordecamethylferrocene.
 15. A process for the preparation of a chargetransfer complex of formula I according to claim 1, which comprisesreacting equimolar amounts of a ferrocene derivative B and apentacenecyanoimine of formula II in an inert solvent.
 16. A compositioncomprising a) a thermosetting, thermoplastic or structurally crosslinkedpolymer, and b) a charge transfer complex of formula I according toclaim 1 in the form of a network of crystal needles in the polymermatrix.
 17. A composition according to claim 16, which contains thecharge transfer complex in an amount of 0.01 to 30% by weight, based onsaid composition.
 18. A composition according to claim 17, whichcontains the charge transfer complex in an amount of 0.01 to 10% byweight.
 19. A composition according to claim 16, wherein thethermoplastic polymer is selected from the group consisting ofpolyolefins, polystyrene, polyvinyl chloride, polyvinylidene chloride,polyvinylidene fluoride, polyacrylates, polymethacrylates, polyamides,polyesters, polycarbonates, aromatic polysulfones, aromatic polyethers,aromatic polyether sulfones, polyimides and polyvinyl carbazole.
 20. Acomposition according to claim 16, wherein the thermosetting polymer isan epoxy resin.
 21. A composition according to claim 16 which is shapedto mouldings, films, foils, fibres or a coating on at least one surfaceof a substrate.
 22. A composition according to claim 21 in the form of alayer on a substrate and the layer thickness of the coating is 0.01 to5000 μm.
 23. A composition according to claim 22, wherein the layerthickness of the coating is 0.1 to 1000 μm.
 24. A process for thepreparation of a composition according to claim 22, which comprises (a)blending a charge transfer complex of formula I into a thermoplasticpolymer, (b) blending a CT complex of formula I with at least onecomponent of a thermosetting or structurally crosslinkable polymer andthen polymerising the blend to a thermosetting or structurallycrosslinked polymer, or (c) dissolving one of a compound of formula IIor a ferrocene derivative B, together with a thermoplastic polymer orwith at least one component of a thermosetting or structurallycrosslinkable polymer in an organic solvent, mixing this solution with asolution of the other one a ferrocene derivative B or a compound offormula II, removing the solvent and polymerising curable mixtures to athermosetting or structurally crosslinked polymer.
 25. A processaccording to claim 24 which can be combined with a shaping process.